EP1287890A1 - Verfahren zur herstellung eines katalysators zur methanreformierung - Google Patents

Verfahren zur herstellung eines katalysators zur methanreformierung Download PDF

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Publication number
EP1287890A1
EP1287890A1 EP00917354A EP00917354A EP1287890A1 EP 1287890 A1 EP1287890 A1 EP 1287890A1 EP 00917354 A EP00917354 A EP 00917354A EP 00917354 A EP00917354 A EP 00917354A EP 1287890 A1 EP1287890 A1 EP 1287890A1
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EP
European Patent Office
Prior art keywords
aluminum
copper
zinc
catalyst
reforming catalyst
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP00917354A
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English (en)
French (fr)
Inventor
Osamu Okada
Mitsuaki Echigo
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Osaka Gas Co Ltd
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Osaka Gas Co Ltd
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Filing date
Publication date
Application filed by Osaka Gas Co Ltd filed Critical Osaka Gas Co Ltd
Publication of EP1287890A1 publication Critical patent/EP1287890A1/de
Withdrawn legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen; Reversible storage of hydrogen
    • C01B3/02—Production of hydrogen; Production of gaseous mixtures containing hydrogen
    • C01B3/32—Production of hydrogen; Production of gaseous mixtures containing hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide or air
    • C01B3/323—Catalytic reaction of gaseous or liquid organic compounds other than hydrocarbons with gasifying agents
    • C01B3/326—Catalytic reaction of gaseous or liquid organic compounds other than hydrocarbons with gasifying agents characterised by the catalysts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
    • B01J21/04—Alumina
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/03—Precipitation; Co-precipitation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/16—Reducing
    • B01J37/18—Reducing with gases containing free hydrogen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
    • C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
    • C01B2203/0233—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a steam reforming step
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041—Composition of the catalyst
    • C01B2203/1076—Copper or zinc-based catalysts
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/12—Feeding the process for making hydrogen or synthesis gas
    • C01B2203/1205—Composition of the feed
    • C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
    • C01B2203/1217—Alcohols
    • C01B2203/1223—Methanol
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Definitions

  • the present invention relates to a method of manufacturing a methanol reforming catalyst, and more particularly relates to a method of manufacturing a highly active and durable catalyst in a technique of manufacturing a reforming gas containing hydrogen as a main ingredient by reacting methanol with steam (or steam and air, depending on cases).
  • precipitation catalysts of e.g. copper, nickel, chrome, zinc and aluminum oxides have been proposed hitherto as described in Patent Publication (Unexamined) H3-52643 and Patent Publication (Unexamined) H5-305234, for example.
  • aluminum nitrate is mainly used as aluminum material and is considered desirable for catalyst production.
  • Methanol reforming catalysts manufactured by a conventional coprecipitation method are unsatisfactory with respect to heat resistance, and the catalyst activity thereof reduces continuously when used for a long time.
  • This drawback is particularly outstanding under conditions of a reaction temperature of about 300°C or higher, and the durability of the catalysts at such temperature is extremely low.
  • This problem is particularly outstanding when aluminum nitrate is used as a source of aluminum as described hereinafter on the basis of test results.
  • reaction temperature may rise even higher.
  • a catalyst durable for a long period of time even when used at a temperature in the order of 300 to 400°C.
  • the object of the present invention is to provide a method of manufacturing a highly active, highly heat resistant and durable methanol reforming catalyst which can be used for a long time even under reaction conditions of 300°C and higher.
  • the characterizing features of a method of manufacturing a methanol reforming catalyst according to the present invention for fulfilling the above object are the first through fifth features described hereinafter.
  • the first feature lies in that, in a method of manufacturing a copper-zinc-aluminum-based methanol reforming catalyst by coprecipitation, a copper compound, a zinc compound and aluminum hydroxide are used and mixed with an alkaline substance by a mixing operation such as stirring to produce a precipitate, and the precipitate obtained is calcined.
  • said calcination preferably, is conducted at a calcination temperature in a range of 300 to 650°C.
  • coprecipitation is employed, however, aluminum hydroxide is used as an aluminum source instead of using aluminum nitrate as used in conventional methods. Further, as in the conventional methods, a coprecipitate of copper, zinc and aluminum is obtained, which is then calcined to produce a predetermined catalyst.
  • calcination temperature when the temperature is lower than 300°C, calcination is insufficient and tends to result in poor heat resistance and durability, and when higher than 650°C, calcination may be excessive. Both cases are undesirable.
  • the third feature in addition to the first and second features it is preferable to make a compounding ratio of copper, zinc and aluminum, in an atomic ratio of metal atoms, 1 : 0.3 to 10 : 0.05 to 2.
  • the calcined product provided by the calcination in the first feature preferably, is reduced by hydrogen at 150°C to, but not exceeding, 300°C.
  • the calcined product provided by the calcination in the first feature preferably, is hydrogen-reduced by hydrogen gas diluted with an inert gas to a hydrogen concentration not exceeding 6%.
  • the particle diameter tends to be increased and the surface area decreased by heat. Further, excessive heat may subtly change the porous structure, which results in a major change in property of the methanol reforming catalyst.
  • the mixed oxide is reduced by hydrogen
  • the reduction can be conducted under mild conditions.
  • the methanol reforming catalyst manufactured according to the invention is superior in durability to conventional catalysts, and therefore is resistant to the heat generated during the reduction process. The reduction can be conducted without so much care as in the conventional methods. This is another advantage of the present application.
  • Fig. 1 is a view showing durability test results of methanol reforming catalysts.
  • a method of manufacturing a copper-zinc-aluminum-based methanol reforming catalyst i.e. a methanol reforming catalyst containing copper, zinc and aluminum oxides as main ingredients
  • a copper-zinc-aluminum-based methanol reforming catalyst i.e. a methanol reforming catalyst containing copper, zinc and aluminum oxides as main ingredients
  • a mixed solution prepared by adding aluminum hydroxide to an aqueous solution containing a copper compound (e.g. copper nitrate or copper acetate) and a zinc compound (e.g. zinc nitrate or zinc acetate), is, while being stirred, dripped into an aqueous solution of an alkaline substance (e.g. sodium carbonate or potassium carbonate) kept at a temperature of about 60°C to produce a precipitate.
  • a copper compound e.g. copper nitrate or copper acetate
  • a zinc compound e.g. zinc nitrate or zinc acetate
  • the process of adding the mixed solution for manufacturing the precipitate can be conducted in a reverse order, that is, copper, zinc and aluminum compounds can be added to the solution of the alkaline substance. Further, aluminum hydroxide can be added to the solution of the alkaline substance in advance, and the solution containing the copper compound and zinc compound can be mixed therein to produce the precipitate.
  • the produced precipitate is sufficiently cleaned with water, then filtered and dried. Next, by calcining this at a temperature in the range of 300 to 650°C, a sintered product of copper oxide-zinc oxide-aluminum oxides is obtained. After an additive (e.g. graphite) is added as necessary, the sintered product obtained is molded into a shape such as of a tablet or an extrusion. It is preferable that the calcination temperature is in the range of 350 to 550°C.
  • the above sintered product has a compounding ratio of copper oxide, zinc oxide and aluminum oxide, in an atomic ratio of metal atoms: copper, zinc, aluminum as 1 : 0.3 to 10 : 0.05 to 2, preferably about 1 0.6 to 3 : 0.3 to 1.
  • the mixed oxide resulting from the above processes is subjected to a hydrogen reduction as necessary.
  • the hydrogen reduction process because of the low melting point of copper, the particle diameter tends to be increased and the surface area decreased by heat. Further, excessive heat may subtly change the porous structure, which results in a major change in property of the methanol reforming catalyst.
  • a gas not involved in the reaction e.g. nitrogen gas, argon gas or methane gas
  • a gas not involved in the reaction e.g. nitrogen gas, argon gas or methane gas
  • an inert gas such as nitrogen gas is suitable for use.
  • the copper-zinc-aluminum-based methanol reforming catalyst provided by the above method has a dense structure consisting of an agglomerate of fine particles. Extremely small copper particles are uniformly dispersed over the surfaces of zinc oxide particles, and maintained in a highly activated state by a chemical interaction with zinc oxide.
  • the aluminum oxide is distributed all over, keeping the copper particles and zinc oxide particles from sintering under the heat, to be in a highly active state.
  • high catalytic activity can be maintained for a long time even at a comparatively high temperature of 300°C or above and under high LHSV conditions.
  • Embodiments of preparing methanol reforming catalysts according to the above technique, and a comparative example according to a conventional technique will be described hereinafter in the order of manufacturing method first and then properties.
  • Aluminum hydroxide is added to an aqueous solution of sodium carbonate and, while keeping the temperature thereof at 60°C, a mixed solution containing copper nitrate and zinc nitrate, while being stirred, is slowly dripped to form a precipitate. Thereafter the precipitate is sufficiently washed, then filtered and dried.
  • Aluminum hydroxide is added to an aqueous solution of sodium carbonate and, while keeping the temperature thereof at 60°C, a mixed solution containing copper nitrate and zinc nitrate, while being stirred, is slowly dripped to form a precipitate. Thereafter the precipitate is sufficiently washed, then filtered and dried.
  • S/C molar ratio of steam/methanol
  • Table 1 shows the catalytic activities at 300°C, 350°C and 400°C of each catalyst obtained (methanol conversion rate, 1 - [CH 3 OH]/((CO 2 ] + [CO] + [CH 3 OH]), where [ ] shows each ingredient concentration in the gas after the reaction).
  • LHSV (methanol feeding rate) 5h -1 Methanol conversion rate (%) 300°C 350°C 400°C Catalyst 1 95.1 98.4 100 Catalyst 2 95.2 100 100 Catalyst 3 93.9 100 100 Catalyst 4 94.8 100 100 Comparative catalyst 1 64.4 89.0 99.7
  • the catalysts manufactured by the invention are found to show higher methanol conversion rates than the comparative catalyst.
  • Catalysts 1 through 4 which are objects of this application, show no decline in the conversion rate, whereas the Comparative Catalyst using aluminum nitrate as aluminum source shows a distinct decline.
  • methanol reforming catalysts of high heat resistance and high activity can be obtained.
  • the catalysts provided have high activity and long life even under the conditions of high reaction temperature and high LHSV (methanol feeding rate).

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Combustion & Propulsion (AREA)
  • Inorganic Chemistry (AREA)
  • Catalysts (AREA)
EP00917354A 2000-04-19 2000-04-19 Verfahren zur herstellung eines katalysators zur methanreformierung Withdrawn EP1287890A1 (de)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/JP2000/002535 WO2001078892A1 (en) 2000-04-19 2000-04-19 Method for preparing catalyst for reforming methanol

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Publication Number Publication Date
EP1287890A1 true EP1287890A1 (de) 2003-03-05

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US (1) US6844292B1 (de)
EP (1) EP1287890A1 (de)
CA (1) CA2406034A1 (de)
WO (1) WO2001078892A1 (de)

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DE10160487A1 (de) * 2001-12-08 2003-06-12 Sued Chemie Ag Katalysator für die Methanolsynthese und andere Reaktionen
US20080016768A1 (en) 2006-07-18 2008-01-24 Togna Keith A Chemically-modified mixed fuels, methods of production and used thereof
RU2500470C1 (ru) * 2012-11-20 2013-12-10 Открытое акционерное общество "Ангарский завод катализаторов и органического синтеза" (ОАО "АЗКиОС") Способ приготовления катализатора для синтеза метанола и конверсии монооксида углерода
US20230398520A1 (en) * 2022-06-09 2023-12-14 Clariant International Ltd High temperature methanol steam reforming catalyst
CN115041174B (zh) * 2022-06-20 2023-09-29 西南化工研究设计院有限公司 一种大型化甲醇制氢装置铜基催化剂的制备方法
CN117582988B (zh) * 2023-11-09 2025-11-28 中国科学院成都有机化学有限公司 一种甲醇水蒸气重整制氢铜基催化剂及其制备方法

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WO2001078892A1 (en) 2001-10-25
US6844292B1 (en) 2005-01-18
CA2406034A1 (en) 2002-10-16

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